Method of producing diamines and polyamines of the diphenylmethane series

ABSTRACT

The invention relates to a method for producing diamines and polyamines of the diphenylmethane series, by condensing aniline and formaldehyde followed by an acid-catalysed rearrangement at different production capacities with alteration of the content of diamines of the diphenylmethane series (altering the binuclear content). Adapting the molar ratio of the total used aniline to the total used formaldehyde and adapting the reaction temperature allows the rearrangement reaction to be fully completed despite the change in dwell time inevitably associated with a change in production capacity, and allows the formation of undesired by-products to be avoided as far as possible; the intended modification to binuclear content is likewise achieved.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a national stage application under 35 U.S.C. § 371 of PCT/EP2017/083264, filed Dec. 18, 2017, which claims the benefit of European Application No. 16206116.2, filed Dec. 22, 2016, both of which are incorporated by reference herein.

FIELD

The present invention relates to a process for preparing di- and polyamines of the diphenylmethane series by condensation of aniline and formaldehyde followed by acid-catalyzed rearrangement at different production capacities with variation of the content of diamines of the diphenylmethane series (change in the bicyclic content). Adjusting the molar ratio of total aniline used to total formaldehyde used and the reaction temperature achieves running of the rearrangement reaction to completion in spite of the change in residence time inevitably associated with the altered production capacity and avoids the formation of unwanted by-products, and also achieves the desired change in the bicyclic content.

BACKGROUND

The preparation of di- and polyamines of the diphenylmethane series (MDA) by reaction of aniline with formaldehyde in the presence of acidic catalysts is known in principle. In the context of the present invention, di- and polyamines of the diphenylmethane series are understood to mean amines and mixtures of amines of the following type:

n here is a natural number≥2. The compounds of this type in which n=2 are referred to hereinafter as diamines of the diphenylmethane series or diaminodiphenylmethanes (MMDA hereinafter; “monomer MDA”). Compounds of this type in which n>2 are referred to in the context of this invention as polyamines of the diphenylmethane series or polyphenylene polymethylene polyamines (PMDA hereinafter; “polymer MDA”). Mixtures of the two types are referred to as di- and polyamines of the diphenylmethane series (for the sake of simplicity referred to hereinafter as MDA). The corresponding isocyanates that can be derived in a formal sense by replacing all NH₂ groups with NCO groups from the compounds of the formula (I) are accordingly referred to as diisocyanates of the diphenylmethane series (MMDI hereinafter), polyisocyanates of the diphenylmethane series or polyphenylene polymethylene polyisocyanates (PMDI hereinafter) or di- and polyisocyanates of the diphenylmethane series (MDI hereinafter). The higher homologs (n>2), both in the case of the amine and in the case of the isocyanate, are generally always present in a mixture with the dimers (n=2), and so only two product types are of relevance in practice, the pure dimers (MMDA/MMDI) and the mixture of dimers and higher homologs (MDA/MDI). The position of the amino groups on the two phenylene groups in the dimers (para-para; ortho-para and ortho-ortho) is specified hereinafter only when it is important. For the sake of simplicity, this is done in the X,Y′-MDA form (4,4′-, 2,4′- or 2,2′-MDA), as is customary in the literature. The same is true of MDI (identification of the isomers as X,Y′-MDI (4,4′-, 2,4′- or 2,2′-MDI).

Industrially, the di- and polyamine mixtures are converted predominantly by phosgenation to the corresponding di- and polyisocyanates of the diphenylmethane series.

The continuous or partly discontinuous preparation of MDA is disclosed, for example, in EP-A-1 616 890, U.S. Pat. No. 5,286,760, EP-A-0 451 442 and WO-A-99/40059. The acidic condensation of aromatic amines and formaldehyde to give di- and polyamines of the diphenylmethane series proceeds in multiple reaction steps. In what is called the “aminal process”, in the absence of an acidic catalyst, formaldehyde is first condensed with aniline to give what is called aminal, with elimination of water. This is followed by the acid-catalyzed rearrangement to MDA in a first step to give para- or ortho-aminobenzylaniline. The aminobenzylanilines are converted to MDA in a second step. Main products of the acid-catalyzed reaction of aniline and formaldehyde are the diamine 4,4′-MDA, its positional isomers 2,4′-MDA and 2,2′-MDA and the higher homologs (PMDA) of the various diamines. In what is called the “neutralization process”, aniline and formaldehyde are converted in the presence of an acidic catalyst directly to aminobenzylanilines, which are then rearranged further to give the bicyclic MMDA isomers and higher polycyclic PMDA homologs. The present invention relates to the aminal process.

Irrespective of the process variant for preparation of the acidic reaction mixture, the workup thereof, according to the prior art, is initiated by neutralization with a base. This neutralization is typically effected at temperatures of, for example, 90° C. to 100° C. without addition of further substances (cf. H. J. Twitchett, Chem. Soc. Rev. 3(2), 223 (1974)). It can alternatively be effected at a different temperature level in order, for example, to accelerate the degradation of troublesome by-products. Hydroxides of the alkali metal and alkaline earth metal elements are suitable as bases. Preference is given to using sodium hydroxide solution.

After the neutralization, the organic phase is separated from the aqueous phase in a separating vessel. The organic phase which comprises crude MDA and remains after removal of the aqueous phase is subjected to further workup steps, for example washing with water (base washing) in order to wash residual salts out of the crude MDA. Finally, the crude MDA thus purified is freed of excess aniline, water and other substances present in the mixture (e.g. solvents) by suitable methods, for example distillation, extraction or crystallization. The workup which is customary according to the prior art is disclosed, for example, in EP-A-1 652 835, page 3 line 58 to page 4 line 13, or EP-A-2 103 595, page 5 lines 21 to 37.

International patent application WO 2014/173856 A1 provides a process for preparing di- and polyamines of the diphenylmethane series by converting aniline and formaldehyde in the absence of an acidic catalyst to aminal and water, removing the aqueous phase and processing the organic aminal phase further to give the di- and polyamines of the diphenylmethane series, in which use of a coalescence aid in the phase separation of the process product obtained in the aminal reaction reduces the proportion of water and hence also of water-soluble impurities in the organic phase comprising the aminal. The di- and polyamines of the diphenylmethane series that are obtained by acid-catalyzed rearrangement and workup after further processing of the aminal phase are of excellent suitability for preparation of the corresponding isocyanates.

The quality of a reaction process for preparation of MDA is defined firstly by the content of unwanted secondary components and impurities in the crude product that can arise from improper conduct of the reaction. Secondly, the quality of a reaction process is defined in that the entire process can be operated without technical production outage or problems that necessitate intervention in the process, and that losses of feedstocks are prevented or at least minimized.

Although the prior art processes described succeed in preparing MDA with a high yield and without loss of quality in the end products, the only processes described are in the normal state of operation. Only a few publications are concerned with states outside normal operation:

International patent application WO 2015/197527 A1 relates to a process for preparing di- and polyamines of the diphenylmethane series (MDA), to a plant for preparation of MDA and to a method of operating a plant for preparation of MDA. The invention enables optimization of production shutdowns in the operation of the MDA process with regard to time taken and optionally also with regard to energy and material consumption by means of what is called a circulation mode in individual plant components. During an interruption in the process or interruption of the operation of individual plant components, there is no introduction of formaldehyde into the reaction, and the plant components that are not affected by an inspection, repair or cleaning measure are operated in what is called circulation mode. What this achieves, among other effects, is that only the plant component in question must be shut down for the period of the measure, which may be advantageous in terms of productivity and economic viability of the process and the quality of the products prepared.

International patent application WO 2015/197519 A1 relates to a process for preparing diamines and polyamines of the diphenylmethane series, in which care is taken during the running-down of the production process that an excess of aniline over formalin is ensured.

International patent application WO 2015/197520 A1 relates to a process for preparing diamines and polyamines of the diphenylmethane series (MDA) from aniline and formaldehyde, in which care is taken during the start-up procedure to ensure that there is a sufficient excess of aniline over formaldehyde which is at least 105% of the molar ratio of aniline to formaldehyde wanted for the target formulation of the MDA to be produced.

Changes in the target production capacity (also called “change in load”) during continuous production (i.e. with a starting state and an end state, in which MDA is produced) are not taken into account here either. Since aniline is typically used in stoichiometric excess, the production capacity of a given plant for preparation of MDA is defined by the formaldehyde feed which, in the context of this invention, is referred to as (formaldehyde) load.

Changes in load are recurrent plant states that have a considerable effect on the economic (and environmentally benign in terms of energy consumption) operation of a continuously operating plant. As well as the “intended” changes in load already mentioned (e.g. reduction in load as a consequence of a fall in demand), there are also changes in load that result inevitably as a consequence of a desired change in the product composition. This is the case, for instance, when achievement of a desired change in the product composition is to significantly increase the ratio of total aniline used to total formaldehyde used (also referred to in the literature as A/F ratio), i.e. significantly more aniline would have to be introduced into the reactor for the same amount of formaldehyde. Since the dimensions of the reactor are fixed, however, it is not possible to increase the amount of aniline arbitrarily. In order to achieve the desired A/F ratio, it may therefore be necessary to reduce the formaldehyde feed and hence the production capacity (the “load”). If the A/F ratio is to be significantly lowered and this is brought about by an increase in the formaldehyde feed—with constant aniline feed—this is inevitably associated with a change in load. In the case of this type of changes in load, there are particular operation-related challenges since two factors of significance for the operation of a production plant—namely firstly the change in load itself, which in continuous production is inevitably associated with a change in residence time, and secondly the desired change in the product composition which, even without a change in load, would entail changes in the reaction parameters—occur simultaneously. This is of course also true when a change in load, in the event of an intended alteration in the product composition, is not necessarily required but is actually desired for other reasons (for example because there is lesser or greater demand for a product of different composition by comparison with the product in the customary composition).

The product composition of a mixture of di- and polyamines of the diphenylmethane series is characterized by two factors in particular, namely:

-   -   1. by the proportion by mass of the diamine of the         diphenylmethane series (MMDA) based on the total mass of di- and         polyamines of the diphenylmethane series (MDA), ω_(MMDA)         hereinafter, (“bicyclic content”) and     -   2. by the isomer distribution within the MMDA content,         which—since 2,2′-MDA is usually present only in minor         proportions—is appropriately described by the proportion by mass         of 2,4′-methylenediphenylenediamine (ω_(2,4′-MDA)) based on the         total mass of diamines of the diphenylmethane series (also         referred to as methylenediphenylenediamines).

The present invention is concerned with a change in the first factor. The proportion by mass of diamines of the diphenylmethane series in the MDA is typically determined by high-performance liquid chromatography (HPLC), which is preferably also employed in the context of the present invention.

It would be desirable to have available a process for preparing di- and polyamines of the diphenylmethane series in which it is possible by simple measures to configure a change in the bicyclic content in conjunction with a change in load such that operation of the process can be continued in an optimized manner (for instance with regard to yield, time taken, energy consumption and avoidance of process-related problems such as caking or blockages in apparatus) in economic, environmental and operational aspects.

SUMMARY

According to the invention, this can be accomplished by a process for preparing di- and polyamines according to patent claim 1. This process, as will be elucidated in detail hereinafter, is more particularly characterized in that the temperature in at least one rearrangement reactor is increased in the event of an intended increase in load and is lowered in the event of an intended decrease in load, and in that, in the case of an intended increase in the bicyclic content, the molar ratio of total aniline used to total formaldehyde used is increased and, in the event of an intended decrease in the bicyclic content, is lowered.

BRIEF DESCRIPTION OF THE DRAWINGS

Various features and characteristics of the inventions described in this specification may be better understood by reference to the accompanying figures, in which:

FIGS. 1a-1c illustrate the procedure of the invention using the example of a decrease in the bicyclic content in conjunction with an increase in load.

FIG. 2 illustrates a production plant suitable for the performance of the process of the invention; and

FIG. 3 shows a detail of the reactor cascade.

DETAILED DESCRIPTION

All configurations of the present invention relate to a process for preparing di- and polyamines of the diphenylmethane series from aniline (1) and formaldehyde (2) in a production plant (10 000), where the molar ratio of total aniline used (1) to total formaldehyde used (2), n(1)/n(2), is always not less than 1.6, comprising the steps of:

(A-I) reacting aniline (1) and formaldehyde (2) in the absence of an acidic catalyst in a reactor (1000, aminal reactor) to obtain a reaction mixture (4) comprising an aminal (3), and then at least partly separating an aqueous phase (6) from the reaction mixture (4) in a removal unit (2000, also called aminal separator) to obtain an organic phase (5) comprising the aminal (3); (A-II) contacting the organic phase (5) which comprises the aminal and is obtained in step (A-I) with an acidic catalyst (7) in a reactor cascade (3000) composed of i reactors j connected in series (3000-j=1, 3000-j=2, . . . , 3000-j=i; hereinafter 3000-1, 3000-2, . . . , 3000-i for short), where i is a natural number from 2 to 10 (acid-catalyzed rearrangement), wherein

-   -   the first reactor (3000-1) in flow direction is operated at a         temperature T₃₀₀₀₋₁ in the range from 25.0° C. to 65.0° C.,         preferably in the range from 30.0° C. to 60.0° C., and is         charged with stream (5) and acidic catalyst (7) and optionally         with further aniline (1) and/or further formaldehyde (2),     -   every reactor downstream in flow direction (3000-2, . . . ,         3000-i) is operated at a temperature of more than 2.0° C. above         T₃₀₀₀₋₁ and is charged with the reaction mixture obtained in the         reactor immediately upstream;         (B) isolating the di- and polyamines of the diphenylmethane         series from the reaction mixture (8-i) obtained from step (A-II)         in the last reactor (3000-i) by at least         (B-I) adding a stoichiometric excess of base (9), based on the         total amount of acidic catalyst used (7), to the reaction         mixture (8-i) obtained in the last reactor (3000-i) in step         (A-II) in a neutralization unit (4000, preferably stirred         neutralization vessel) to obtain a reaction mixture (10),         especially observing a molar ratio of base (9) to total acidic         catalyst used (7) in the range from 1.01 to 1.30         (neutralization);         (B-II) separating the reaction mixture (10) obtained in step         (B-I) in a separation unit (5000, neutralization separator) into         an organic phase (11) comprising di- and polyamines of the         diphenylmethane series and an aqueous phase (12).

The expressions “total aniline used” and “total formaldehyde used” each refer to the total amount of these reactants used in the process according to the invention, i.e. including any proportions additionally added after step (A-I).

The organic phase (11) can, as described in detail hereinafter, be subjected to further workup.

According to the invention, the abovementioned steps are conducted continuously, meaning that the respective reactants are supplied continuously to the apparatus assigned to the respective step and the products are withdrawn continuously therefrom.

According to the invention, the procedure is then that, in the event of a change in load, the temperature in at least one of the reactors 3000-2, . . . , 3000-i and the molar ratio of total aniline used to total formaldehyde used (n(1)/n(2) hereinafter) are adjusted in the manner still to be outlined in detail further down. What this achieves is that, in spite of altered residence time, the rearrangement reaction runs to completion and increased by-product formation as a consequence of the change in load is largely avoided, with achievement of the desired change in the bicyclic content. Adjustment of the temperature in the first reactor in flow direction (3000-1) is not absolutely necessary; however, in the case of this reactor, slightly greater deviations from the temperature before the change in load are permitted during the change in load. These slightly greater tolerances in the temperature during the change in load allow easier control over the change in load in terms of control technology. The tolerances permitted in accordance with the invention, which are still to be elucidated in detail further down, however, are still within such a scope that operational problems are largely to completely avoided.

This procedure allows advantageous configuration of changes in load in conjunction with a desired change in the bicyclic content in economic, environmental (from the point of view of energy consumption) and operational aspects.

Since the invention relates to changes in load, i.e. to different states of operation of a production plant, the following definitions of terms that are used hereinafter are helpful:

Starting state A of the production plant with a given production capacity defined by the amount of formaldehyde introduced:

-   -   mass flow rate m₁ of total aniline used in the starting state:         m₁(A)≠0 [e.g. in t/h],     -   mass flow rate m₂ of total formaldehyde used in the starting         state: m₂(A)≠0 [e.g. in t/h],     -   mass flow rate m₇ of total acidic catalyst used in the starting         state: m₇(A)≠0 [e.g. in t/h],     -   molar ratio n(1)/n(2) of total aniline used (1) to total         formaldehyde used (2) in the starting state: n(1)/n(2)(A),     -   molar ratio n(7)/n(1) of total acidic catalyst used to total         aniline used (often also expressed as protonation         level=n(7)/n(1) 100%) in the starting state: n(7)/n(1)(A), and     -   proportion by mass ω_(MMDA), based on the total mass of di- and         polyamines of the diphenylmethane series, of diamines of the         diphenylmethane series in the starting state: ω_(MMDA)(A).

End state E of the production plant with a target production capacity defined by the amount of formaldehyde introduced (with introduction of less or more formaldehyde compared to the starting state):

-   -   mass flow rate of total aniline used in the end state: m₁(E)≠0         [e.g. in t/h],     -   mass flow rate of total formaldehyde used in the end state:         m₂(E)≠0 [e.g. in t/h],     -   mass flow rate of total acidic catalyst used in the end state:         m₇(E)≠0 [e.g. in t/h],     -   molar ratio of total aniline used (1) to total formaldehyde used         (2) in the end state: n(1)/n(2)(E),     -   molar ratio of total acidic catalyst used to total aniline used         in the end state: n(7)/n(1)(E), and     -   proportion by mass ω_(MMDA), based on the total mass of di- and         polyamines of the diphenylmethane series, of diamines of the         diphenylmethane series which is the target proportion for the         end state: ω_(MMDA)(E).

Transition state T between starting state and end state (corresponding to the period of the change in load):

-   -   mass flow rate of total aniline used in the transition state:         m₁(T)≠0 [e.g. in t/h],     -   mass flow rate of total formaldehyde used in the transition         state: m₂(T)≠0 [e.g. in t/h],     -   mass flow rate of total acidic catalyst used in the transition         state: m₇(T)≠0 [e.g. in t/h],     -   molar ratio n(1)/n(2) of total aniline used (1) to total         formaldehyde used (2) in the transition state: n(1)/n(2)(T),     -   molar ratio n(7)/n(1) of total acidic catalyst used (7) to total         aniline used in the transition state: n(7)/n(1)(T),     -   proportion by mass ω_(MMDA), based on the total mass of di- and         polyamines of the diphenylmethane series, of diamines of the         diphenylmethane series in the transition state: ω_(MMDA)(T).

According to the invention, the transition state begins as soon as m₂ is increased or lowered proceeding from m₂(A) (this time is referred to hereinafter as t₁), and it ends as soon as m₂ reaches the target value for m₂(E) (this time is referred to hereinafter as t₂). At the end of the transition state thus defined (i.e. at t=t₂), the operating parameter n(1)/n(2) is established such that, under the boundary conditions of the changed load, the prerequisites for the production of the MDA product exist with the target altered bicyclic content ω_(MMDA)(E) for the end state, meaning that further MDA is produced from then on with the desired bicyclic content ω_(MMDA)(E). Therefore, at t=t₂: n(1)/n(2)(T)=n(1)/n(2)(E). Since, however, product mixture that was produced before t₂ is still present in the reactors (and to some degree, according to the duration of the transition state and the residence time in the reactors, even product that was produced before t₁), the product composition actually present at the exit from the last reactor (3000-i) in the reactor cascade (3000) corresponds to the target bicyclic content ω_(MMDA)(E) for the end state only after a further period of time Δt has elapsed (generally in the order of magnitude of hours to a few days). Thus, there is a period of time after attainment of t₂ within which the bicyclic content that actually exists in the exit from the last reactor (3000-i) (which is an average of the varying product compositions during the transition state) differs from the target end value ω_(MMDA)(E). However, no later than when all reactors of the reactor cascade (3000) have been flushed through with MDA having the target bicyclic content ω_(MMDA)(E), the bicyclic content actually present at the exit from the last reactor (3000-i) will correspond to the value of ω_(MMDA)(E). This time is referred to hereinafter as t₃. Preferably, the period of time Δt=t₃−t₂ is at most 72 hours, more preferably at most 48 hours, most preferably at most 24 hours.

On the basis of the minimum value for n(1)/n(2) of 1.6 used in the process of the invention, the yield of MDA target product is limited by the flow rate of total formaldehyde used (2) which is introduced. The maximum possible flow rate of total formaldehyde used (2) for preparation of a particular product type (i.e. a mixture of di- and polyamines of the diphenylmethane series characterized by a particular isomer composition of MMDA and a particular ratio of MMDA to PMDA) under the given boundary conditions of the production plant (10 000):

-   -   m₂(N) [e.g. in t/h],         is referred to here and hereinafter as nameplate load.

The maximum possible flow rate of total formaldehyde used (2) may vary according to the MDA product type to be prepared. If the nameplate load in the end state should differ significantly from that in the starting state, it is the nameplate load in the starting state m₂(N, A) that is crucial for the purposes of the present invention (i.e. more particularly for the purpose of quantification of the change in load; for details see below). The value of m₂(N, A) for a given production plant is either known from the outset (for example because the plant was designed for the production of a particular amount of a particular product type per hour) or can be easily determined by the person skilled in the art from the known boundary conditions of the plant (number and size of apparatuses present and the like) for the known operating parameters of the crucial starting state (n(1)/n(2)(A), n(7)/n(1)(A)). In practice, rather than m₂(N), the corresponding product flow rate of MDA (e.g. in t/h) which is to be expected under the assumption of the design parameters for the production plant (including n(1)/n(2) ratio, n(7)/n(1) ratio etc.) is frequently reported. Rather than nameplate load, reference is therefore also frequently made to nameplate production capacity or else nameplate capacity for short. In this connection, the terms “load” and “(production) capacity” ultimately mean the same thing, but have different reference points (flow rate of starting material in one case and flow rate of target product to be expected from this starting material in the other case).

The actual load (or—see the above elucidations—the actual production capacity or capacity for short) in the starting state and end state, defined by the actual mass flow rate of total formaldehyde used in the starting state or end state, can then be expressed in relation to the nameplate load as follows: m ₂(A)=X(A)·m ₂(N) [e.g. in t/h]; m ₂(E)=X(E)·m ₂(N) [e.g. in t/h].

In both cases, X is a dimensionless multiplier greater than 0 and less than or equal to 1 that expresses the actual load in relation to the nameplate load. In the event of a change from production at half the nameplate load (“half-load”) to production with nameplate load (“full load”), accordingly, X(A)=½ and X(E)=1. In the case of increases in load, X(E)>X(A); in the case of reductions in load, X(E)<X(A).

A quantitative measure for the size of a change in load is the magnitude of the differential of X(E) and X(A): |X(E)−X(A)|(=|X(A)−X(E)|)=ΔX

In the context of this invention, a change in load is one with a value of ΔX of not less than 0.10, preferably of not less than 0.15, more preferably of not less than 0.20, most preferably of not less than 0.25. The process of the invention comprises at least one change in load as thus defined.

The process of the invention also comprises at least one change in the bicyclic content. In the context of this invention, a change in the bicyclic content is one where the target end value of the bicyclic content, ω_(MMDA)(E), is as follows:

ω_(MMDA)(E)≥1.05·ω_(MMDA)(A), preferably ω_(MMDA)(E)≥1.10ω_(MMDA)(A), more preferably ω_(MMDA)(E)≥1.15·ω_(MMDA)(A) (increase in the bicyclic content) or

ω_(MMDA)(E)≤0.95·ω_(MMDA)(A), preferably ω_(MMDA)(E)≤0.90·ω_(MMDA)(A), more preferably ω_(MMDA)(E)≤0.85·ω_(MMDA)(A) (lowering of the bicyclic content).

The bicyclic content ω_(MMDA) here is always the bicyclic content in the MDA that exits from the last reactor (3000-i) of the reactor cascade (3000).

In all abovementioned states of operation, n(1)/n(2) is set to a value of not less than 1.6. With regard to the expression “total acidic catalyst used”, the statements made above for aniline and formaldehyde are correspondingly applicable: what is meant is the total amount of acidic catalyst. This can be (and is preferably) fed entirely to the reactor 3000-1; alternatively, it is possible to supply this reactor with just the majority of the total acidic catalyst used and to meter smaller proportions additionally into the reactors that follow in flow direction.

According to the invention, the temperature in the first reactor in flow direction (3000-1) is always chosen such that it is within the range from 25.0° C. to 65.0° C., preferably 30.0° C. to 60.0° C. This is true in all states of operation, i.e. in the starting state, transition state and end state.

According to the invention, moreover, the temperature in each of the reactors downstream in flow direction (3000-2, 3000-3, . . . 3000-i) is set to a value more than 2.0° C. above T₃₀₀₀₋₁. This is also true in all states of operation, i.e. in the starting state, transition state and end state.

According to the invention, the molar ratio of total acidic catalyst used to total aniline used, n(7)/n(1), in the end state differs from that in the starting state by a maximum of 10%, preferably by a maximum of 5%, i.e.: 0.90·n(7)/n(1)(A)≤n(7)/n(1)(E)≤1.10·n(7)/n(1)(A), preferably 0.95·n(7)/n(1)(A)≤n(7)/n(1)(E)≤1.05·n(7)/n(1)(A).

During the transition state T (i.e. within the period from t₁ to t₂), greater differences from the starting state can be permitted. In this case: 0.85·n(7)/n(1)(A)≤n(7)/n(1)(T)≤1.15·n(7)/n(1)(A), preferably 0.90·n(7)/n(1)(A)≤n(7)/n(1)(T)≤1.10·n(7)/n(1)(A);

No later than at the end of the transition state, i.e. at the time at which m₂ has reached the target value for m₂(E) (time t₂), however, the difference, as outlined above, should be limited to not more than 10%, preferably not more than 5%. More preferably, the ratio n(7)/n(1) in the end state is adjusted to the same value as in the starting state (i.e. n(7)/n(1)(E)=n(7)/n(1)(A)), and only in the transition state is a value differing from the starting state within the above-defined limits permitted where applicable.

Moreover, during the transition state T:

(i) the temperature in the first reactor in flow direction (3000-1) from step (A-II) is set to a value that differs from the temperature in this reactor during the starting state A by a maximum of 10.0° C., preferably by a maximum of 5.0° C., more preferably by a maximum of 2.0° C., the particularly preferred maximum deviation by ±2.0° C. being regarded as the same temperature for all practical purposes (in the context of the present invention, slight nominal deviations from a temperature in the region of up to ±2.0° C. are considered to be—essentially—the same temperature; changes of greater than 2.0° C., by contrast, are considered to be significant temperature changes); (ii-1) in the case that m₂(E)>m₂(A), the temperature in at least one of the reactors downstream in flow direction (3000-2, . . . , 3000-i), by comparison with the starting state A, is increased by more than 2.0° C., and so the target end temperature is reached at least at the time at which m₂ has reached the target value for m₂(E) (i.e. at t=t₂), and in all reactors (3000-2, . . . , 3000-i) in which the temperature is not increased it is kept the same within a range of variation of ±2.0° C.; (ii-2) in the case that m₂(E)<m₂(A), the temperature in at least one of the reactors downstream in flow direction (3000-2, . . . , 3000-i), by comparison with the starting state A, is lowered by more than 2.0° C., and so the target end temperature is reached at least at the time at which m₂ has reached the target value for m₂(E) (i.e. at t=t₂), and in all reactors (3000-2, . . . , 3000-i) in which the temperature is not lowered it is kept the same within a range of variation of ±2.0° C.; (iii-1) in the case that ω_(MMDA)(E)≥1.05·ω_(MMDA)(A), n(1)/n(2)(T) is adjusted such that, at the time at which m₂ has reached the target value for m₂(E) (i.e. at t=t₂): 1.05·n(1)/n(2)(A)≤n(1)/n(2)(T)≤2.00·n(1)/n(2)(A), preferably 1.10·n(1)/n(2)(A)≤n(1)/n(2)(T)≤1.60·n(1)/n(2)(A); where it is always the case throughout the transition state prior to attainment of time t₂ that: 0.80·n(1)/n(2)(A)≤n(1)/n(2)(T)≤2.50·n(1)/n(2)(A), preferably 0.90·n(1)/n(2)(A)≤n(1)/n(2)(T)≤2.00·n(1)/n(2)(A); (iii-2) in the case that ω_(MMDA)(E)≤0.95·ω_(MMDA)(A), n(1)/n(2)(T) is adjusted such that, at the time at which m₂ has reached the target value for m₂(E) (i.e. at t=t₂): 0.50·n(1)/n(2)(A)≤n(1)/n(2)(T)≤0.95·n(1)/n(2)(A), preferably 0.60·n(1)/n(2)(A)≤n(1)/n(2)(T)≤0.90·n(1)/n(2)(A) where it is always the case throughout the transition state prior to attainment of time t₂ that: 0.40·n(1)/n(2)(A)≤n(1)/n(2)(T)≤2.50·n(1)/n(2)(A), preferably 0.50·n(1)/n(2)(A)<n(1)/n(2)(T)≤2.00·n(1)/n(2)(A).

According to the invention, for the reactor 3000-1 during the transition state, a significant deviation from the temperature in the starting state is possible. In this reactor, changes in the amount of heat released as a consequence of the change in load are manifested to an enhanced degree. (Significant contributions to exothermicity are firstly the heat of neutralization which is released in the reaction of the acid with the aminic components of the reaction mixture, and the acid-catalyzed rearrangement of the aminal that sets in.) This can be taken into account if required by greater tolerances in the temperature in the transition state. However, it is preferable, at the end of the transition state (i.e. when m₂ has reached the target value for m₂(E); time t₂), to adjust the temperature in the reactor 3000-1 back to a value which corresponds to that of the starting state within a range of variation of ±2.0° C.

The increase in temperature in at least one of the reactors 3000-2, . . . , 3000-i in the case of an increase in load should be undertaken very rapidly in order to be able to compensate for the shortening of the residence time in the best possible way. Preferably, the target temperature for the end state is already established as the new target temperature at t₁, such that the actual existing temperature assumes the target value for the end state within the shortest possible time, but no later than at t₂.

The decrease in temperature in at least one of the reactors 3000-2, . . . , 3000-i in the case of a decrease in load, by contrast, should be undertaken very slowly in order to avoid the formation of unrearranged products. Preferably, the target temperature for the end state is not attained until t₂.

It is essential to the invention that, at the end of the transition state (i.e. when the target load for the end state has been established), in the case of a rise in the bicyclic content, the molar ratio of total aniline used to total formaldehyde used (n(1)/n(2)) is increased compared to the starting state. In the case of a decrease in the bicyclic content, the procedure is reversed (lowering of n(1)/n(2)). In principle, a change in the bicyclic content can be associated either with an increase in load or with a decrease in load. Depending on the starting situation, however, there can be preferred combinations:

Especially when the load in the starting state, m₂(A), is already at a value close to the nameplate load or even equal to the nameplate load, it is preferable—under some circumstances, as described at the outset, even required—to combine a desired increase in the bicyclic content (i.e. in the case that ω_(MMDA)(E)≥1.05·ω_(MMDA)(A)) with a decrease in load.

The reverse case, the combination of a decrease in the bicyclic content (i.e. in the case that ω_(MMDA)(E)≤0.95·ω_(MMDA)(A)) with an increase in load, may also be preferable, namely when, because of the lowering of the ratio n(1)/n(2) associated with the decrease in the bicyclic content, there is more scope available for an increase in the load (and this is associated with a corresponding demand for the target product). It will be appreciated that the selection of the combination of change in load and change in bicyclic content is highly dependent on the starting state: if the load m₂ in the starting state is, for example, already just 50% of the nameplate load (called “half-load”), the aim, irrespective of the desired change in the bicyclic content, will generally be to increase the load (unless the demand for the product with altered composition is very low).

The procedure of the invention is illustrated in FIG. 1a-c using the example of a decrease in the bicyclic content in conjunction with an increase in load. This and the other drawings are merely intended to illustrate the basic principle of the invention and do not make any claim to be true to scale. In FIG. 1a-c , the bicyclic content ω_(MMDA) is plotted as a function of time t. In the starting state A with given values for the operating parameters n(1)/n(2)=n(1)/n(2)(A) and m₂=m₂(A) (and also—not shown—n(7)/n(1)=n(7)/n(1)(A)), ω_(MMDA) corresponds to the starting value ω_(MMDA)(A). As a result of the inventive changes in the operating parameters in the transition state that are elucidated in detail in the paragraph which follows (beginning at t=t₁ and ending at t=t₂), ω_(MMDA) decreases over the course of time to the end value ω_(MMDA)(E). The end values for the operating parameters n(1)/n(2) and m₂ are attained at t₂. At t₂, the prerequisites thus exist for the production of further MDA with the desired bicyclic content ω_(MMDA)(E). As elucidated above in connection with the definition of the transition state, however, the composition of the MDA actually present in the exit from the last reactor (3000-i) of the reactor cascade (3000) only reaches this target end value ω_(MMDA)(E) some time after t₂, namely at t₃. The latter is of course true not just for the illustrative cases shown in FIG. 1a-c but for all conceivable combinations of change in load and change in the bicyclic content, i.e., for example, even in the event of an intended rise in ω_(MMDA).

In the starting state, the load m₂=m₂(A). At time t=t₁ (=commencement of the transition state), the load is increased until, at time t=t₂ (=end of the transition state), it reaches the target value for the end state m₂=m₂(E); in other words—and for all conceivable configurations of the invention and not just cases shown by way of example in FIG. 1a-c —m₂(t=t₂)=m₂(E) and n(1)/n(2)(T)(t=t₂)=n(1)/n(2)(E). The lowering of n(1)/n(2) may, as shown in FIG. 1a , be continuous. However, this is not obligatory; for example, it is also possible, as shown in FIG. 1b , first to increase n(1)/n(2) (by increasing m₁ to a greater degree at first than m₂) and only to lower it to the target end value with a time delay, which leads to an intermediate rise in n(1)/n(2). All that is essential is that the target end value for the ratio n(1)/n(2) is established during the transition state in such a way that this target end value n(1)/n(2)=n(1)/n(2)(E) is reached at time t=t₂ (i.e. at the time at which m₂ has reached the target value for m₂(E)). This is not restricted to the case of lowering of the bicyclic content in conjunction with an increase in load, as shown by way of example in FIG. 1a-c , but is also true of all conceivable combinations of change in load and change in the bicyclic content. The target end value n(1)/n(2)(E) can be established stepwise or, as shown in FIG. 1a-c , continuously, preference being given to continuous establishment. The respectively required adjustments in the operating parameter m₂ and if required m₁ and/or m₇ are preferably commenced at the same time and more preferably conducted in such a way that the target values in each case for the end of the change in load (i.e. the time at which m₂ has reached the target value for m₂(E)) are established via continuous adjustment of the respective operating parameter.

However, a slight time delay (generally in the order of magnitude of seconds, preferably not more than 15 seconds) is possible in the required adjustments of m₁ and m₂. This is especially effected in such a way that, in the case of an increase in load, it commences first with the adjustment of m₁ (if such an adjustment, generally an increase, is required) and only then is m₂ increased with a slight time delay, in such a way that the requirements of the invention on the ratio n(1)/n(2) are complied with. In the case of a decrease in load, the reverse procedure is followed (commencement with the adjustment (i.e. in this case lowering) of m₂, and optionally adjustment, generally lowering, of m₁, again of course with the proviso that the requirements of the invention on the ratio n(1)/n(2) are complied with). If, in this embodiment, an increase in load is commenced with an increase in m₁ before the increase in m₂ is commenced, there is already a rise in the n(1)/n(2) ratio shortly before t=t₁ (i.e. shortly before commencement of the transition state as defined in accordance with the invention). It is generally the case that, when commencing with an adjustment of m₁ before commencement of the desired change (increase in load or decrease in load) of m₂ (such a time is shown in FIGS. 1c and 1s identified there by to), the ratios n(1)/n(2)(A) and n(7)/n(1)(A), for the purposes of the present invention, are calculated on the basis of the value of m₁ before commencement of the adjustment of m₁ (cf. FIG. 1c ).

Embodiments of the invention are described in detail hereinafter. These embodiments, unless stated otherwise in the specific case, are applicable to all process regimes of the invention. It is possible here to combine various embodiments with one another as desired, unless the opposite is apparent to the person skilled in the art from the context.

FIG. 2 shows a production plant (10 000) suitable for the performance of the process of the invention.

FIG. 3 shows a detail of the reactor cascade (3000). The merely optional addition of further acidic catalyst (7) to the reactors (3000-2) to (3000-i) downstream of the reactor (3000-1) is shown by dotted arrows.

Step (A-I) of the process of the invention, provided that the other requirements of the invention are complied with, can be conducted as known in principle from the prior art. Aniline and aqueous formaldehyde solution are preferably condensed here at molar ratios in the range from 1.6 to 20, preferably 1.6 to 10 and more preferably 1.6 to 6.0, even more preferably of 1.7 to 5.5 and very exceptionally preferably of 1.8 to 5.0, at temperatures of 20.0° C. to 120.0° C., preferably 40.0° C. to 110.0° C. and more preferably 60.0° C. to 100.0° C., to give aminal and water. The reactor of step (A-I) is operated at standard pressure or under elevated pressure. There is preferably a pressure of 1.05 bar to 5.00 bar (absolute), very preferably of 1.10 bar to 3.00 bar and most preferably of 1.20 bar to 2.00 bar (absolute). The pressure is maintained by pressure-regulating valves, or by connecting the offgas systems of aminal reactor (1000) and the overflow from the aminal separator (2000) used for phase separation on completion of reaction. The aminal separator and the outlet for the aqueous phase are preferably heated in order to prevent caking.

Suitable aniline qualities are described, for example, in EP 1 257 522 B1, EP 2 103 595 A1 and EP 1 813 598 B1. Preference is given to using technical grade qualities of formalin (aqueous solution of formaldehyde) with 30.0% by mass to 50.0% by mass of formaldehyde in water. However, formaldehyde solutions with lower or higher concentrations or else the use of gaseous formaldehyde are also conceivable.

The phase separation of organic aminal phase and aqueous phase is preferably effected at temperatures of 20.0° C. to 120.0° C., more preferably of 40.0° C. to 110.0° C. and most preferably of 60.0° C. to 100.0° C., in each case preferably at ambient pressure or at slightly elevated pressure relative to ambient pressure (elevated by up to 0.10 bar) be carried out.

Step (A-II) of the process of the invention, provided that the other requirements of the invention are complied with, can be conducted as known in principle from the prior art. The aminal is rearranged in the presence of an acidic catalyst, typically a strong mineral acid such as hydrochloric acid. Preference is given to the use of mineral acid in a molar ratio of mineral acid to aniline of 0.0010 to 0.90, preferably 0.050 to 0.50. It is of course also possible to use solid acidic catalysts as described in the literature. Formaldehyde can be added here to a mixture of aniline and acidic catalyst, and the reaction solution can be fully reacted by stepwise heating. Alternatively, aniline and formaldehyde can first be pre-reacted and then, with or without prior removal of water, admixed with the acidic catalyst or a mixture of further aniline and acidic catalyst, and then the reaction solution is fully reacted by stepwise heating. This reaction can be executed continuously or batch-wise by one of the numerous methods described in the literature (for example in EP 1 616 890 A1 or EP 127 0544 A1).

It is possible to supply the first reactor 3000-1 with further aniline and/or further formaldehyde. It is likewise possible to supply the downstream reactors 3000-2, . . . , 3000-i with small amounts of aniline and/or formaldehyde. These may each be fresh feedstocks or recycle streams from other reactors. However, the majority of total aniline used and of total formaldehyde used is introduced into the “aminal reactor” 1000. Regardless of how aniline (1) and formaldehyde (2) are distributed, optionally over various reactors, the process of the invention is preferably conducted in such a way that the molar ratio of total aniline used (1) to total formaldehyde used (2), n(1)/n(2), in all states of operation (A, T, E) always has a value of 1.6 to 2.0, preferably of 1.6 to 10 and more preferably of 1.6 to 6.0, even more preferably of 1.7 to 5.5 and very exceptionally preferably of 1.8 to 5.0.

Preferably, all the acidic catalyst used (7) is fed completely to reactor 3000-1. Alternatively, it is possible to feed a portion of the total acidic catalyst used (7) to one or more of the downstream reactors 3000-2, . . . , 3000-i in flow direction.

The acidic catalyst (7) used in the process of the invention is preferably a mineral acid, especially hydrochloric acid. Suitable hydrochloric acid qualities are described, for example, in EP 1 652 835 A1.

Suitable reactors 3000-1, 3000-2, . . . 3000-i in step (A) in both process regimes are apparatuses known to those skilled in the art, such as stirred tanks and tubular reactors:

In the case of stirred tank reactors, the temperature is generally the same throughout the reactor contents, and so, for the purposes of the present invention, it does not matter where the temperature is measured. If, contrary to expectation, significant temperature differences exist through the reactor contents, the temperature measured at the exit of the reaction mixture from the reactor is the crucial temperature for the purposes of the present invention.

If there is a significant temperature gradient between entry of the reaction mixture into the reactor and exit of the reaction mixture from the reactor, as may be the case in tubular reactors, the temperature measured at the exit of the reaction mixture from the reactor is the crucial temperature for the purposes of the present invention.

Preferably, the temperature in the reactors of the reactor cascade 3000 increases from reactor 3000-1 to reactor 3000-i, i.e. the temperature in the last reactor 3000-i is preferably higher than in the first reactor 3000-1, and the temperature in two successive reactors between 3000-1 and 3000-i may also be the same, but the temperature of each reactor 3000-2, 3000-3, . . . , 3000-i is not lower than that of the preceding reactor. Preferably, however, the temperature in the reactors of the reactor cascade 3000 increases successively from reactor 3000-1 to reactor 3000-i, i.e. the temperature of each reactor 3000-2, 3000-3, . . . , 3000-i is higher than that of the preceding reactor.

It is likewise preferable to set

-   -   T₃₀₀₀₋₁ always to a value of 25.0° C. to 65.0° C., more         preferably 30.0° C. to 60.0° C., and     -   the temperature in each of the reactors downstream in flow         direction (3000-2, . . . , 3000-i) always to a value of 35.0° C.         to 200.0° C., more preferably of 50.0° C. to 180.0° C.

This makes it possible, in reactor 3000-1, to achieve a practicable compromise between the aim of minimum by-product formation, especially with regard to N-methyl- and N-formyl-MDA, on the one hand (promoted by lower temperature) and the aim of ensuring a viscosity of the reaction mixture that assures practicable processibility of the product on the other hand (promoted by higher temperature).

All the aforementioned figures for preferred temperatures are applicable in all states of operation (A, T, E).

The respective values of n(1)/n(2), n(7)/n(1) and of the temperature of each reactor j of the reactor cascade T_(3000-j) at the end of the transition state (i.e. when m₂ has reached the target value for the end state m₂(E)) are preferably retained for the duration of production with the formaldehyde mass flow rate m₂(E). At the temperature T_(3000-j), in the terminology of the present invention, as already mentioned, slight variations within the range of ±2.0° C. are still considered to be the same temperature.

Step (B-I), provided that the other requirements of the invention are complied with, can be conducted as known in principle from the prior art. The reaction mixture comprising the di- and polyamines of the diphenylmethane series is optionally neutralized with addition of water and/or aniline. According to the prior art, the neutralization is typically effected at temperatures of, for example, 90.0° C. to 120.0° C. without addition of further substances. It can alternatively be effected at a different temperature level in order, for example, to accelerate the degradation of troublesome by-products. Suitable bases are, for example, the hydroxides of the alkali metal and alkaline earth metal elements. Preference is given to employing aqueous NaOH. The base used for neutralization is preferably used in amounts of greater than 100%, more preferably 105% to 120%, of the amount stoichiometrically required for the neutralization of the acidic catalyst used (see EP 1 652 835 A1).

Step (B-II), provided that the other requirements of the invention are complied with, can be conducted as known in principle from the prior art. The neutralized reaction mixture comprising the di- and polyamines of the diphenylmethane series is separated into an organic phase comprising di- and polyamines of the diphenylmethane series and an aqueous phase. This can be assisted by the addition of aniline and/or water. If the phase separation is assisted by addition of aniline and/or water, they are preferably added already with vigorous mixing in the neutralization. The mixing can be effected here in mixing zones with static mixers, in stirred tanks or stirred tank cascades, or else in a combination of mixing zones and stirred tanks. The neutralized reaction mixture diluted by addition of aniline and/or water is then preferably supplied to an apparatus which, owing to its configuration and/or internals, is particularly suitable for separation into an organic phase comprising MDA and an aqueous phase, preferably phase separation or extraction apparatuses according to the prior art, as described, for example, in Mass-Transfer Operations, 3rd Edition, 1980, McGraw-Hill Book Co, p. 477 to 541, or Ullmann's Encyclopedia of Industrial Chemistry (Vol. 21, Liquid-Liquid Extraction, E. Müller et al., pages 272-274, 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, DOI: 10.1002/14356007.b03_06.pub2) or in Kirk-Othmer Encyclopedia of Chemical Technology (see “http://onlinelibrary.wiley.com/book/10.1002/0471238961”, Published Online: 15 Jun. 2007, pages 22-23) (mixer-settler cascades or settling vessels).

If, in step (A-II), during the transition state, the flow rate of acidic catalyst is increased significantly, the flow rate of base used in step (B-I) will of course also be increased correspondingly (and within the same timeframe), in order that the requirement of the invention for the stoichiometric excess of base is always fulfilled, i.e. even in the transition state. If, in step (A-II), during the transition state, the flow rate of acidic catalyst is lowered significantly, the flow rate of base used in step (B-I) will preferably also be lowered correspondingly (and likewise within the same timeframe), in order to avoid unnecessary salt burdens.

Step (B-II) is preferably followed by further workup steps, namely:

Step (B-III): washing the organic phase (11) in a scrubbing unit (6000, “washing vessel”) with washing liquid (13), followed by

Step (B-IV): separating the mixture (14) obtained in step (B-III) in a separation unit (7000, “washing water separator”) into an organic phase (16) comprising di- and polyamines of the diphenylmethane series and an aqueous phase (15);

Step (B-V): distilling the organic phase (16) from step (B-IV) in a distillation apparatus (8000) to obtain the di- and polyamines of the diphenylmethane series (18), with removal of a stream (17) comprising water and aniline.

These steps can be conducted as known in principle from the prior art. In particular, it is preferable to conduct these steps continuously (as defined above) as well.

It is particularly preferable that there is a subsequent washing (B-III) of the organic phase (11) with water (13) and a new separation of the water phase (15) for removal of residual salt contents (preferably as described in DE-A-2549890, page 3). After exiting from the phase separation in step (B-IV), the organic phase (16) comprising di- and polyamines of the diphenylmethane series typically has a temperature of 80.0° C. to 150.0° C.

Water and aniline are separated by distillation from the organic phase thus obtained, comprising di- and polyamines of the diphenylmethane series, as described in EP 1 813 597 B1. The organic phase preferably has a composition, based on the mass of the mixture, of 5.0% to 15% by mass of water and, according to the use ratios of aniline and formaldehyde, 5.0% to 90% by mass, preferably 5.0% to 40% by mass, of aniline and 5.0% to 90% by mass, preferably 50% to 90% by mass, of di- and polyamines of the diphenylmethane series.

More preferably, the process of the invention also includes a further step (C) in which recycling of stream (17) comprising water and aniline, optionally after workup, into step (A-I) and/or, if the optional addition of further aniline (1) in step (A-II) is conducted, into step (A-II) is undertaken.

In all embodiments of the invention, the setting of the operating parameters to the target values for the end state is concluded with the end of the change in load (i.e. as soon as the mass flow rate of total formaldehyde used m₂ has reached the target value for the end state m₂(E); time t₂). The values of n(1)/n(2) and of the temperature in each reactor of the reactor cascade (3000) are therefore set stepwise or continuously, preferably continuously, to the target values for the end state. The same applies for the value n(7)/n(1), provided that this value is changed. In the case of stepwise setting of the respective parameter, the setting preferably comprises multiple stages, meaning that, for example, a target end temperature is established via one or more intermediate values, each of which is maintained for a particular period of time, between the starting temperature and the target end temperature. The term “continuous setting” also encompasses the case that the respective parameter is first varied in the “opposite direction”, as shown in FIG. 1b -c.

In all embodiments of the invention, it is further preferable to restrict the change in load and the change conducted in parallel in the operating parameters crucial for the bicyclic content to a time not exceeding 120 minutes, i.e. to limit the period within which the mass flow rate of total formaldehyde used m₂ is adjusted proceeding from m₂(A) to the target value for the end state m₂(E) (=duration of the transition state=period of time from ti to t₂) is preferably to 120 minutes. The minimum duration of the transition state is preferably 1.00 minute, more preferably 5.00 minutes and most preferably 30.00 minutes. The envisaged change in the operating parameters crucial to the bicyclic content takes place within the same period of time.

Detailed configurations of the invention are elucidated in detail in the appended examples.

The di- and polyamines of the diphenylmethane series that are obtained in accordance with the invention can be reacted by the known methods, under inert conditions, with phosgene in an organic solvent to give the corresponding di- and polyisocyanates of the diphenylmethane series, the MDI. The phosgenation can be conducted here by any of the methods known from the prior art (e.g. DE-A-844896 or DE-A-19817691).

The procedure of the invention gives rise to the following advantages for the preparation of MDA:

-   i) The productivity of the MDA plant is higher because the     occurrence of off-spec material is minimized -   ii) There is lower formation of by-products with acridine and     acridane structure and/or N-formyl- and N-methyl-MDA. Higher     proportions of these by-products can lead to quality problems in the     MDI conversion product.

Thus, the procedure of the invention, during a non-steady state (during the transition state), enables a technically seamless change in load in conjunction with a change in the bicyclic content without subsequent outage periods in the steady state (the end state) that follows with constantly high quality of the desired MDA end product. The process of the invention enables rapid performance of a change in load associated with a change in the bicyclic content and hence rapid reaction to events such as raw material shortage, altered demands on the product composition, etc.

EXAMPLES

The results outlined in the examples for the bicyclic content, the isomer composition and the content of N-methyl-4,4′-MDA are based on calculations. The calculations are based partly on theoretical models and partly on process data collected in real operational experiments, the statistical evaluation of which created a mathematical correlation of running parameters and result (e.g. bicyclic content). The content of N-formyl-4,4′-MDA is reported on the basis of operational experience values. All percentages and ppm values reported are proportions by mass based on the total mass of the respective stream of matter. The proportions by mass in the real operational experiments that gave the basis for the theoretical model were ascertained by HPLC.

Reactor temperatures are based on the temperature of the respective process product at the exit from the reactor.

The MDA prepared, in all examples, has a residual aniline content in the range from 50 ppm to 100 ppm and a water content in the range from 200 ppm to 300 ppm.

A. Reduction in Load Proceeding from Production with Nameplate Load

I. Starting State: Description of the Conditions Chosen for the Preparation of MDA at Nameplate Load

In a continuous reaction process, 23.20 t/h of feed aniline (containing 90.0% by mass of aniline, 1) and 9.60 t/h of 32% aqueous formaldehyde solution (corresponding to a molar ratio of aniline (1):formaldehyde (2) of 2.25:1) are mixed and converted to the aminal (3) at a temperature of 90.0° C. and a pressure of 1.40 bar (absolute) in a stirred reaction tank (1000). The reaction tank is provided with a cooler having a cooling circuit pump. The reaction mixture leaving the reaction tank is guided into a phase separation apparatus (aminal separator, 2000) (step (A-I)).

After the phase separation to remove the aqueous phase (6), the organic phase (5) is admixed in a mixing nozzle with 30% aqueous hydrochloric acid (7) (protonation level 10%, i.e. 0.10 mol of HCl is added per mole of amino groups) and run into the first rearrangement reactor (3000-1). The first rearrangement reactor (called “vacuum tank”) is operated at 50.0° C., which is ensured by means of evaporative cooling in a reflux condenser at a pressure of 104 mbar (absolute). The reflux condenser is charged with 0.50 t/h of fresh aniline. The rearrangement reaction is conducted to completion in a reactor cascade composed of a total of seven reactors at 50.0° C. to 156.0° C. (i.e. 50.0° C. in reactor 3000-1/60.0° C. in reactor 3000-2/83.0° C. in reactor 3000-3/104.0° C. in reactor 3000-4/119.0° C. in reactor 3000-5/148.0° C. in reactor 3000-6/156.0° C. in reactor 3000-7) (step (A-II)).

On completion of reaction, the reaction mixture (8-i) obtained is admixed with 32% sodium hydroxide solution in a molar ratio of 1.10:1 sodium hydroxide to HCl and reacted in a stirred neutralization vessel (4000) (step (B-I)). The temperature here is 115.0° C. The absolute pressure is 1.40 bar. The neutralized reaction mixture (10) is then separated in a neutralization separator (5000) into an aqueous lower phase (12), which is guided to a wastewater collection vessel, and into an organic phase (11) (step (B-II)).

The organic upper phase (11) is guided to the washing and washed with condensate (13) in a stirred washing vessel (6000) (step (B-III)). After the washing water (15) has been separated from the biphasic mixture (14) obtained in the washing vessel (6000) in a washing water separator (7000, step (B-IV)), the crude MDA (16) thus obtained is freed of water and aniline (removed together as stream 17) by distillation, and 17.00 t/h of MDA (18) were obtained as bottom product (step (B-V)).

MDA prepared in this way has an average composition of 45.2% 4,4′-MDA, 5.5% 2,4′-MDA, 0.3% 2,2′-MDA, i.e. a total bicyclic content of 51.0% and also 0.3% N-methyl-4,4′-MDA and 0.3% N-formyl-4,4′-MDA, the remainder to 100% consisting essentially of higher homologs (PMDA) and isomers thereof.

II. Target End State: Production at Half-Load

Example 1 (Comparative Example)

reduction in load of the MDA plant from nameplate load to half-load (=50% of nameplate load), where the n(1)/n(2) ratio and the n(7)/n(1) ratio are kept the same, the aniline, formalin, hydrochloric acid and sodium hydroxide solution feedstocks are reduced simultaneously and the temperatures in the vacuum tank (3000-1), the downstream reactors and the exit temperature of the crude MDA solution in the last rearrangement reactor (3000-7) remain the same

The MDA plant, as described above under A.I, is operated at a production capacity of 17.00 t/h of MDA. Now the bicyclic content is to be increased to about 62%, combined with halving of the load owing to lower product demand. For this purpose, at the same time, the feed rates of aniline and formalin to the aminal reactor (1000) are adjusted to the new production load within 120 minutes. The formalin rate is reduced to 4.80 t/h. The aniline feed rate is reduced to 11.35 t/h. At the same time, the flow rate of hydrochloric acid into the mixing nozzle in the feed to the first rearrangement reactor (3000-1) is halved. The first rearrangement reactor is still operated at 50.0° C., which is ensured by means of the evaporative cooling in the reflux condenser at 104 mbar (absolute). The reflux condenser is still charged with 0.50 t/h of fresh aniline. The rearrangement reaction is conducted to completion in a reactor cascade at 50.0° C. to 156.0° C. (50.0° C. in reactor 3000-1/60.0° C. in reactor 3000-2/83.0° C. in reactor 3000-3/104.0° C. in reactor 3000-4/119.0° C. in reactor 3000-5/148.0° C. in reactor 3000-6/156.0° C. in reactor 3000-7). On completion of reaction, the reaction mixture obtained, as described in the general conditions for preparation of MDA, is neutralized with sodium hydroxide solution, with reduction of the amount of sodium hydroxide solution within the same time window as formalin and aniline, and then worked up to give MDA (18).

40 hours after commencement of the change in load, the MDA in the feed to the MDA tank has a composition of 44.7% 4,4′-MDA, 5.2% 2,4′-MDA, 0.2% 2,2′-MDA, i.e. a total bicyclic content of 50.1%, and also 0.3% N-methyl-4,4′-MDA and 0.3% N-formyl-4,4′-MDA, the remainder to 100% consisting essentially of higher homologs (PMDA) and isomers thereof. The MDA has an elevated proportion of unwanted by-products with acridine and acridane structure. In this regard, see also section C further down. The bicyclic content is essentially the same as that in the starting state.

Example 2 (Inventive)

reduction in load of the MDA plant from nameplate load to reduced load, where the n(1)/n(2) ratio is increased, the aniline and formalin feedstocks are reduced simultaneously and where the n(7)/n(1) ratio is kept the same, hydrochloric acid and sodium hydroxide solution are reduced simultaneously with the aniline and formalin feedstocks, the temperature in the vacuum tank (3000-1) remains the same and the exit temperature of the crude MDA solution in the last rearrangement reactor (3000-7) is lowered

The MDA plant, as described above under A.I, is operated at a production capacity of 17.00 t/h of MDA. Now the bicyclic content is to be increased to about 62%, combined with a reduction in the load to slightly less than half the load in the starting state owing to lower product demand. For this purpose, at the same time, the feed rates of aniline and formalin to the aminal reactor (1000) are adjusted to the new production load within 120 minutes. The formalin rate is reduced to 4.60 t/h. The aniline feed rate is reduced to 14.60 t/h. The flow rate of hydrochloric acid into the mixing nozzle in the feed to the first rearrangement reactor is adjusted within the same period as aniline and formalin with retention of the protonation level of 10%. The first rearrangement reactor (3000-1) is still operated at 50.0° C., which is ensured by means of the evaporative cooling in the reflux condenser at 104 mbar (absolute). The reflux condenser is still charged with 0.50 t/h of fresh aniline. The rearrangement reaction is conducted to completion in a reactor cascade at 50.0° C. to 146.0° C. (50.0° C. in reactor 3000-1/60.0° C. in reactor 3000-2/81.0° C. in reactor 3000-3/95.0° C. in reactor 3000-4/115.0° C. in reactor 3000-5/143.0° C. in reactor 3000-6/146.0° C. in reactor 3000-7) (step (A-II)). On completion of reaction, the reaction mixture obtained, as described in the general conditions for preparation of MDA, is neutralized with sodium hydroxide solution, with reduction of the amount of sodium hydroxide solution within the same time window as formalin and aniline and HCl with retention of the molar ratio of 1.10:1 sodium hydroxide solution to HCl, and then worked up to give the desired MDA type, obtaining 8.50 t/h of MDA (18) as the bottom product from the distillation.

40 hours after commencement of the change in load, the MDA in the feed to the MDA tank has a composition of 54.3% 4,4′-MDA, 7.5% 2,4′-MDA, 0.3% 2,2′-MDA, i.e. a total bicyclic content of 62.1% and also 0.2% N-methyl-4,4′-MDA and 0.2% N-formyl-4,4′-MDA, the remainder to 100% consisting essentially of higher homologs (PMDA) and isomers thereof. The product differs corresponds to the desired target product. An elevated proportion of unwanted by-products with acridine and acridane structure is not formed.

TABLE 1 Comparison of the examples from section A End state End state Half-load Reduced load Starting state Example 1 Example 2 Nameplate load (comp.) (inv.) Aniline (90%) in reactor 1000 [t/h] 23.20 11.35 14.60 Aniline in reactor 3000-1 [t/h] 0.50 0.50 0.50 Formalin (32%) in reactor 1000 [t/h] 9.60 4.80 4.60 n(1)/n(2) 2.25 2.25 2.99 [n(1)/n(2)(T)(t = t₂)]/[n(1)/n(2)(A)] — 1.00 1.33 Protonation level [%] 10 10 10 n(7)/n(1) 0.10 0.10 0.10 Temp. gradient in reactor cascade 50.0 → 156.0 50.0 → 156.0 50.0 → 146.0 3000 [° C.] T(3000-1) [° C.] 50.0 50.0 50.0 T(3000-2) [° C.] 60.0 60.0 60.0 T(3000-3) [° C.] 83.0 83.0 81.0 T(3000-4) [° C.] 104.0 104.0 95.0 T(3000-5) [° C.] 119.0 119.0 115.0 T(3000-6) [° C.] 148.0 148.0 143.0 T(3000-7) [° C.] 156.0 156.0 146.0 Production capacity [t/h] 17.00 8.50 8.50 4,4′-MDA [%] 45.2 44.7 54.3 2,4′-MDA [%] 5.5 5.2 7.5 2,2′-MDA [%] 0.3 0.2 0.3 N-methyl-MDA [%] 0.3 0.3 0.2 N-formyl-MDA [%] 0.3 0.3 0.2 Bicyclic content [%] 51.0 50.1 62.1 Comment — Elevated As desired, proportion of product has an unwanted by- increased bicyclic products with content and a acridine and similar by-product acridane spectrum to the structure; bicyclic product in the content virtually starting state unchanged B. Increase in Load Proceeding from Production at Half-Load I. Starting State: Description of the Conditions Chosen for the Preparation of MDA at Half-Load

(N.B. There are of course various options for operating a production plant 10 000 at half-load.) The conditions set in example 2 are one option; for examples 3 and 4 which follow, another option was chosen for the “half-load” starting state.)

The reaction is operated as described above under A.I for nameplate load with the following differences:

11.35 t/h of feed aniline (containing 90.0% by mass of aniline);

4.80 t/h of 32% aqueous formaldehyde solution (i.e. the molar ratio of aniline:formaldehyde is 2.25:1);

50.0° C. in reactor 3000-1/60.0° C. in reactor 3000-2/81.0° C. in reactor 3000-3/95.0° C. in reactor 3000-4/116.0° C. in reactor 3000-5/144.0° C. in reactor 3000-6/146.0° C. in reactor 3000-7;

Bottom product of 8.50 t/h of MDA (18).

MDA prepared in this way has an average composition of 46.3% 4,4′-MDA, 5.0% 2,4′-MDA, 0.2% 2,2′-MDA, i.e. a total bicyclic content of 51.5% and also 0.3% N-methyl-4,4′-MDA and 0.3% N-formyl-4,4′-MDA, the remainder to 100% consisting essentially of higher homologs (PMDA) and isomers thereof.

II. Target End State: Production at Nameplate Load

Example 3 (Comparative Example)

increase in load of the MDA plant from half-load to nameplate load (nameplate load based on an MDA having 62% bicyclic content), where the n(1)/n(2) ratio is increased and the n(7)/n(1) ratio is kept the same, the aniline, formalin, hydrochloric acid and sodium hydroxide solution feedstocks are increased simultaneously and the temperatures in the vacuum tank (3000-1), the downstream reactors and the exit temperature of the crude MDA solution in the last rearrangement reactor (3000-7) remain the same

The MDA plant, as described above under B.I, is operated at a production capacity of 8.50 t/h of MDA. Now the bicyclic content is to be increased to about 62%, combined with an increase in the load to the nameplate load possible for such a product of m₂=7.20 t/h owing to higher product demand. For this purpose, at the same time, the feed rates of aniline and formalin to the aminal reactor are adjusted to the new production load within 120 minutes. The formalin rate is increased to 7.20 t/h. The aniline feed rate is increased to 23.20 t/h. The flow rate of hydrochloric acid into the mixing nozzle in the feed to the first rearrangement reactor is increased within the same period as aniline and formalin with retention of the protonation level of 10% (i.e. with retention of the n(7)/n(1) ratio). The first rearrangement reactor (3000-1) is still operated at 50.0° C., which is ensured by means of the evaporative cooling in the reflux condenser at 104 mbar (absolute). The reflux condenser is charged with 0.50 t/h of fresh aniline. The rearrangement reaction is still conducted to completion in the reactor cascade at 50.0° C. to 146° C. (50.0° C. in reactor 3000-1/60.0° C. in reactor 3000-2/82.0° C. in reactor 3000-3/94.0° C. in reactor 3000-4/116.0° C. in reactor 3000-5/144.0° C. in reactor 3000-6/146.0° C. in reactor 3000-7).

After the reaction, the reaction mixture obtained is admixed with 32% sodium hydroxide solution in a molar ratio of 1.10:1 sodium hydroxide solution to HCl and reacted in a stirred neutralization vessel, increasing the amount of sodium hydroxide solution within the same time window as formalin, aniline and HCl with retention of the molar ratios. The further workup is effected as described above under A.I. At the end of the transition state, 13.3 t/h of a bottom product are obtained.

Result: “MDA” thus prepared has not been completely rearranged and still contains partly rearranged products such as aminobenzylanilines, which lead to quality problems in the subsequent phosgenation to give MDI, for example distinctly elevated color values in the resulting MDI product. The MDA thus prepared, and also the resulting MDI, are off-spec product.

Example 4 (Inventive)

Increase in load of the MDA plant from half-load to nameplate load (nameplate load based on an MDA having 62% bicyclic content), where the n(1)/n(2) ratio is increased, the aniline and formalin feedstocks are increased simultaneously, and where the n(7)/n(1) ratio is kept the same, hydrochloric acid and sodium hydroxide solution are increased simultaneously, the temperature in the vacuum tank (3000-1) is kept the same and the exit temperature of the crude MDA solution in the last rearrangement reactor (3000-7) is increased

The MDA plant, as described above under B.I, is operated at a production capacity of 8.50 t/h of MDA. Now the bicyclic content of the product is to be increased to about 62%, and this altered product is to be produced with its specific maximum possible production capacity owing to higher product demand. For this purpose, at the same time, the feed rates of aniline and formalin to the aminal reactor are adjusted to the new production load within 120 minutes. The formalin rate is increased to 7.20 t/h. The aniline feed rate is increased to 23.20 t/h. The flow rate of hydrochloric acid into the mixing nozzle in the feed to the first rearrangement reactor is adjusted within the same period as aniline and formalin with retention of the protonation level of 10%. The first rearrangement reactor (3000-1) is still operated at 50.0° C., which is ensured by means of the evaporative cooling in the reflux condenser at 104 mbar (absolute). The reflux condenser is charged with 0.50 t/h of fresh aniline. The rearrangement reaction is conducted to completion in the reactor cascade at 50.0° C. to 156° C. (50.0° C. in reactor 3000-1/60.0° C. in reactor 3000-2/83.0° C. in reactor 3000-3/104.0° C. in reactor 3000-4/119.0° C. in reactor 3000-5/148.0° C. in reactor 3000-6/156.0° C. in reactor 3000-7) (step A-II)).

After the reaction, the reaction mixture obtained is admixed with 32% sodium hydroxide solution in a molar ratio of 1.10:1 sodium hydroxide solution to HCl and reacted in a stirred neutralization vessel, increasing the amount of sodium hydroxide solution within the same time window as formalin, aniline and hydrochloric acid. The temperature is 115.0° C. The absolute pressure is 1.40 bar. The further workup is effected as described further up under A.I. At the end of the transition state, the bottom product obtained is 13.30 t/h of MDA (18).

20 hours after commencement of the change in load, the MDA in the feed to the MDA tank has a composition of 53.6% 4,4′-MDA, 7.8% 2,4′-MDA, 0.4% 2,2′-MDA, i.e. a total bicyclic content of 61.8% and also 0.2% N-methyl-4,4′-MDA and 0.3% N-formyl-4,4′-MDA, the remainder to 100% consisting essentially of higher homologs (PMDA) and isomers thereof. The product differs only insignificantly from the MDA stream (18) which is obtained on average in the starting state as described in B.I. An elevated proportion of unwanted by-products with acridine and acridane structure is not formed.

TABLE 2 Comparison of the examples from section B End state End state Nameplate load of Nameplate load of Starting state the target product the target product Half-load Example 3 (comp.) Example 4 (inv.) Aniline (90%) in reactor 1000 [t/h] 11.35 23.20 23.20 Aniline in reactor 3000-1 [t/h] 0.50 0.50 0.50 Formalin (32%) in reactor 1000 [t/h] 4.80 7.20 7.20 n(1)/n(2) 2.25 2.99 2.99 [n(1)/n(2)(T)(t = t₂)]/[n(1)/n(2)(A)] — 1.33 1.33 Protonation level [%] 10 10 10 n(7)/n(1) 0.10 0.10 0.10 Temp. gradient in reactor cascade 50.0 → 146.0 50.0 → 146.0 50.0 → 156.0 3000 [° C.] T(3000-1) [° C.] 50.0 50.0 50.0 T(3000-2) [° C.] 60.0 60.0 60.0 T(3000-3) [° C.] 81.0 82.0 83.0 T(3000-4) [° C.] 95.0 94.0 104.0 T(3000-5) [° C.] 116.0 116.0 119.0 T(3000-6) [° C.] 144.0 144.0 148.0 T(3000-7) [° C.] 146.0 146.0 156.0 Production capacity [t/h] 8.50 13.30 13.30 4,4′-MDA [%] 46.3 — 53.6 2,4′-MDA [%] 5.0 — 7.8 2,2′-MDA [%] 0.2 — 0.4 N-methyl-MDA [%] 0.3 — 0.2 N-formyl-MDA [%] 0.3 — 0.3 Bicyclic content [%] 51.5 — 61.8 Comment — MDA has not been As desired, completely product has an rearranged and still elevated bicyclic contains partly content and a rearranged similar by-product products such as spectrum to the aminobenzylanilines product in the which lead to starting state quality problems in the subsequent phosgenation to give MDI, for example distinctly elevated color values C. Fundamental Experiments for Formation of by-Products with Acridine and Acridane Structure

In a series of experiments, the amount of aqueous 30% hydrochloric acid required in each case to achieve the desired protonation level (see table 3 below) was added to a 2,2′-MDA solution in aniline preheated to 100.0° C. The 2,2′-MDA concentration in each of the individual experiments was 1.0% by mass; in addition, the solutions contained octadecane as an internal standard for gas chromatography (GC) analysis. The resulting mixture was transferred as quickly as possible by means of a peristaltic pump to a Büchi glass autoclave preheated to 120.0° C. and heated to the reaction temperature envisaged (see table 3). On attainment of the desired reaction temperature, the first sample was taken (time=zero). In order to monitor the progress of the reaction, further samples were taken after 30, 60, 120 and 240 minutes and analyzed by means of GC analysis. Reaction conditions and experimental results are collated in table 3 below.

TABLE 3 Laboratory experiments for formation of the acridane and acridine secondary components Sum total Reaction Protonation (acridine + temperature level Time acridane) Experiment [° C.] [%] [min] [ppm] 1 160° C. 10% 15 79 30 208 60 421 120 925 240 1775 2 170° C. 25% 0 977 30 2554 60 3950 120 5647 240 8894 3 160° C. 25% 0 364 30 930 60 1594 120 2681 240 4354 4 180 10% 0 606 30 1630 60 2613 120 3932 240 5294 5 170 10% 0 292 30 794 60 1533 120 2406 240 3932 6 160  5% 0 0 30 0 60 0 120 0 240 0 7 170  5% 0 0 30 0 60 0 120 0 240 218 8 180  5% 0 0 30 402 60 834 120 1355 240 2380

It is found that, with rising temperature and rising hydrochloric acid concentration, the formation of the acridine and acridane secondary components from 2,2′-MDA occurs to an increased degree. 

The invention claimed is:
 1. A process for preparing di- and polyamines of the diphenylmethane series from aniline (1) and formaldehyde (2) in a production plant (10 000), where the molar ratio of total aniline used (1) to total formaldehyde used (2), n(1)/n(2), is always not less than 1.6, comprising: (A-I) reacting aniline (1) and formaldehyde (2) in the absence of an acidic catalyst to obtain a reaction mixture (4) comprising an aminal (3), and then at least partly separating an aqueous phase (6) from the reaction mixture (4) to obtain an organic phase (5) comprising the aminal (3); (A-II) contacting the organic phase (5) which comprises the aminal and is obtained in step (A-I) with an acidic catalyst (7) in a reactor cascade (3000) composed of i reactors connected in series (3000-1, 3000-2, . . . , 3000-i), where i is a natural number from 2 to 10, wherein the first reactor (3000-1) in flow direction is operated at a temperature T3000-1 in the range from 25.0° C. to 65.0° C. and is charged with stream (5) and acidic catalyst (7) and optionally with further aniline (1) and/or further formaldehyde (2), and every reactor downstream in flow direction (3000-2, . . . , 3000-i) is operated at a temperature of more than 2.0° C. above T₃₀₀₀₋₁ and is charged with the reaction mixture obtained in the reactor immediately upstream; (B) isolating the di- and polyamines of the diphenylmethane series from the reaction mixture (8-i) obtained from step (A-II) in the last reactor (3000-i) by a process comprising: (B-I) adding a stoichiometric excess of base (9), based on the total amount of acidic catalyst used (7), to the reaction mixture (8-i) obtained in the last reactor (3000-i) in step (A-II) to obtain a reaction mixture (10); and (B-II) separating the reaction mixture (10) obtained in step (B-I) into an organic phase (11) comprising di- and polyamines of the diphenylmethane series and an aqueous phase (12); wherein in the event of a change in the production capacity from a starting state A with a mass flow rate ml of total aniline used in the starting state of m1(A)≠0, a mass flow rate m₂ of total formaldehyde used in the starting state of m₂(A)=X(A)·m₂(N), where X(A) is a dimensionless number >0 and ≤1 and m₂(N) denotes the nameplate load of the production plant (10 000), a molar ratio n(1)/n(2) of total aniline used (1) to total formaldehyde used (2) in the starting state of n(1)/n(2)(A), a molar ratio n(7)/n(1) of total acidic catalyst used to total aniline used in the starting state of n(7)/n(1)(A) and a proportion by mass ω_(MMDA), based on the total mass of di- and polyamines of the diphenylmethane series, of diamines of the diphenylmethane series of ω_(MMDA)(A) to an end state E with a mass flow rate ml of total aniline used of in the end state m₁(E)≠0, a mass flow rate m₂ of total formaldehyde used in the end state of m₂(E)=X(E)·m₂(N), where X(E) is a dimensionless number >0 and ≤1, a molar ratio n(1)/n(2) of total aniline used (1) to total formaldehyde used (2) in the end state of n(1)/n(2)(E), a molar ratio n(7)/n(1) of total acidic catalyst used to total aniline used in the end state of n(7)/n(1)(E) and a target proportion by mass ω_(MMDA), based on the total mass of di- and polyamines of the diphenylmethane series, of diamines of the diphenylmethane series for the end state of ω_(MMDA)(E) by a quantity ΔX=|X(E)−X(A)|, with ΔX≥0.10, wherein the process comprises at least one change in production capacity that commences at a time t₁ and has concludes at a time t₂, wherein ω_(MMDA) is also altered in such a way that, for the target value of ω_(MMDA)(E) for the end state, either ≥1.05·ω_(MMDA)(A) or ≤0.95·ω_(MMDA)(A), and wherein: 0.90·n(7)/n(1)(A)≤n(7)/n(1)(E)≤1.10·n(7)/n(1)(A); characterized in that, in the period from t₁ to t₂, the transition state T, with a molar ratio of total aniline used (1) to total formaldehyde used (2) of n(1)/n(2)(T) and a molar ratio of total acidic catalyst used to total aniline used of n(7)/n(1)(T), (i) the temperature in the first reactor (3000-1) in flow direction from step (A-II) is adjusted to a value that differs from the temperature in that reactor during the starting state A by not more than 10.0° C.; (ii-1) in the case that m₂(E)>m₂(A), the temperature in at least one of the reactors downstream in flow direction (3000-2, . . . , 3000-i), by comparison with the starting state A, is increased by more than 2.0° C. in such a way that the target end temperature is reached no later than at time t₂, and in all reactors (3000-2, . . . , 3000-i) in which the temperature is not increased it is kept the same within a range of variation of ±2.0° C.; (ii-2) in the case that m₂(E)<m₂(A), the temperature in at least one of the reactors downstream in flow direction (3000-2, . . . , 3000-i), by comparison with the starting state A, is lowered by more than 2.0° C. in such a way that the target end temperature is reached no later than at time t₂, and in all reactors (3000-2, . . . , 3000-i) in which the temperature is not lowered it is kept the same within a range of variation of ±2.0° C.; (iii-1) in the case that ω_(MMDA)(E)≥1.05·ω_(MMDA)(A), n(1)/n(2)(T) is adjusted such that, at time t₂: 1.05·n(1)/n(2)(A)≤n(1)/n(2)(T)≤2.00·n(1)/n(2)(A); where it is always the case throughout the transition state prior to attainment of time t₂ that: 0.80·n(1)/n(2)(A)≤n(1)/n(2)(T)≤2.50·n(1)/n(2)(A); (iii-2) in the case that ω_(MMDA)(E)≤0.95·ω_(MMDA)(A), n(1)/n(2)(T) is adjusted such that, at time t₂: 0.50·n(1)/n(2)(A)≤n(1)/n(2)(T)≤0.95·n(1)/n(2)(A) where it is always the case throughout the transition state prior to attainment of time t₂ that: 0.40·n(1)/n(2)(A)≤n(1)/n(2)(T)≤2.50·n(1)/n(2)(A).
 2. The process of claim 1, in which the temperature in the reactors of the reactor cascade 3000 increases from reactor 3000-1 to reactor 3000-i in all states of operation (A, T, E).
 3. The process of claim 1, in which it is always the case that T₃₀₀₀₋₁ is set to a value in the range from 25.0° C. to 65.0° C. and the temperature in each of the reactors downstream in flow direction (3000-2, . . . , 3000-i) is set to a value in the range from 35.0° C. to 200.0° C.
 4. The process of claim 3, in which it is always the case that T₃₀₀₀₋₁ is set to a value in the range from 30.0° C. to 60.0° C. and the temperature in each of the reactors downstream in flow direction (3000-2, . . . , 3000-i) is set to a value in the range from 50.0° C. to 180.0° C.
 5. The process claim 1, in which the acidic catalyst (7) is a mineral acid.
 6. The process claim 1, in which step (B) further comprises: (B-III) washing the organic phase (11) with washing liquid (13); (B-IV) separating the mixture (14) obtained in step (B-III) into an organic phase (16) comprising di- and polyamines of the diphenylmethane series and an aqueous phase (15); and (B-V) distilling the organic phase (16) from step (B-IV) to obtain the di- and polyamines of the diphenylmethane series (18), with removal of a stream (17) comprising water and aniline.
 7. The process of claim 6, additionally comprising: (C) recycling stream (17), optionally after workup, into step (A-I) and/or, if the optional addition of further aniline (1) in step (A-II) is conducted, into step (A-II).
 8. The process claim 1, in which, in the case that ω_(MMDA)(E)≥1.05·ω_(MMDA)(A), m₂(E) is lowered relative to m₂(A).
 9. The process of claim 1, in which, in the case that ω_(MMDA)(E)≤0.95·ω_(MMDA)(A), m₂(E) is increased relative to m₂(A).
 10. The process claim 1, in which the molar ratio of total aniline used (1) to total formaldehyde used (2), n(1)/n(2), in all states of operation (A, T, E) is adjusted to a value of 1.6 to
 20. 11. The process claim 1, in which the values of n(1)/n(2), n(7)/n(1) and of the temperature of each reactor j of the reactor cascade (3000), T_(3000-j), that exist in each case at time t₂ are retained for the duration of the production with the formaldehyde mass flow rate m₂(E).
 12. The process of claim 1, in which, throughout the transition state T prior to attainment of time t₂, the following is true of the molar ratio of total acid catalyst used to total aniline used n(7)/n(1)(T): 0.85·n(7)/n(1)(A)≤n(7)/n(1)(T)≤1.15·n(7)/n(1)(A).
 13. The process of claim 10, in which at time t₂: n(7)/n(1)(E)=n(7)/n(1)(A).
 14. The process of claim 1, in which the target end value for the molar ratio of total aniline used to total formaldehyde used, n(1)/n(2)(E) is established by continuously adjusting the value of m₂ and at least one of the values of ml and/or m₇ until time t₂.
 15. The process of claim 1, in which the period from ti to t₂ lasts from 1.00 minute to 120 minutes. 